Manufacture of phenol



Jan..15, L1946. I F. Pom-ERA y 2,392,875

MANUFACTURE OF PHNOL Filed Feb. 21, 1941 3 Sheets-Sheet 1 ATTORNE s sne'ets-sheeta Filed Feb. 21, 1941 yINVENTOR fran/' Parier TTORNEY Patented 125, 1956 MANUFACTURE or rnENoi.

Frank Porter, Syracuse, N. Y., assigner to The Solvay ProcesslCompany, New York, N. Y., a Y corporationof -New York Application February 21, 1941, Serial No. 379,923

`6 Claims. (,Cl. 260-621) This` invention relates to the manufacture of phenol by the vapor phase oxidationv of benzene. 1n United States Patent 2,223,383 of Wendell W. Moyer and William C. Klingelhoefer there is described a process for the manufacture of phenol from benzene.

benzene in vapor phase with air or other gas vcontaining molecular oxygen and passing the* mixture through a space reactor V,atan elevated temperature to oxidize a -minor proportion of the f `benzene to'phenol. Y Y l The. adaptation of this'process to manufacture of phenol on alarge scale presents diiiiculties.`

First, thegfdesired reaction proceeds at -prac- The process comprises mixing the ticable' rates only athgh temperatures `or vat highpre res. Highpressureoperations entailv v the-.po ty of leakage and `consequent danger of inury as a result of exposure of Workmen to poisonous fumes. For a maximum of safety in conducting theprocess it is accordingly desirable to employ reactionV pressures near or below atmospheric pressure. At pressures in the vicinity of atmospheric pressure, reaction temperatures most suitable from the standpoint of phenol yield and plant capacity lie between 600 and 800 C. It will be appreciated that at these high temperatures most materials commonly lemployed for constructing reaction equipment are unsuitable.

Second, even if the reaction is controlled so that less than of the benzene used is oxidized, the reaction generates suiicient heat to raise the temperature of the reaction mixture upwards of 300 C. This inlitself would not be a serious problem but for the fact that not only phenol formation but a number of sidereactions take place at greatly accelerated rates as the temperature is increased. The degree of oxidation may be limited by controlling the proportion of oxidizing gas but the' side reactions continue even in the absence of oxygen. The relationship of reactionrate and temperature for the main oxidation and for the side reactions demandsvactomarily used to control hydrocarbon oxidations.

'2. Finally, the oxidation process seems to be. aly lergic in various degrees to all of thecustomary control must be combined with effective removal of heat of reaction.

'Ihe present invention has for an object the conduct of the vapor phase oxidation of benzene to phenol on a commercial scale in such a manner and in an apparatus of such design that the problems of reaction temperature control and'heat removal are eectively solved using ordinary structural materials lreadily available.

In accordance with the present invention the vapor phase oxidation of benzene to phenol is conducted by passing a reaction mixture comprising benzene vapor and oxygen through a reaction zone defined by heat cumulative material and periodically reversing the flow vof reaction mixture through the reaction zone. It has been found that the reaction may be eectively controlled in such an apparatus to produce, on a large scale, yields of phenol substantially equal to those obtained in laboratory tests in carefully regulated small scale laboratory equipment.

In order 'that the invention may be employed yeffectively it is advisable to follow several general rules in the design of the reaction equipment. It has been found, for example. that. the reaction zone should be in the form of an elongated chamber or chambers such that the ratio of mass velocity, MV, expressed as pounds of reaction mixture per hour per square foot of cross-sec- SVznu, expressed as cubic feet of gas at standard temperature and pressure (0 C., 760 mm.) per cubic foot of reaction space per hour, is at least 2. It is especially important that the MV/SVao ratio benumerically at least 1.4.1 The subscripts concerned. SVso is the space velocity calculated on that part of the reactorvwithin 80 centigrade degrees of the maximum average reactor temperature and SVm is the space velocity calculated on thatvpart of the reactor within 200 centigradev ldegrees of the maximum average reactor temperature. f

In general for large scaleoperations it is prei ierred Vthat the reactor have a passage length of flat least 40 feet. For example, the reactor may construction materials and those materials least injurious to phenol yields are not such as are normally regarded as suitable for connstructionV vof reaction equipment where accurate temperature have a single passage 1 to 2 inches wide and 100 to 2 00 feet long, or several such passages in parallel. It is not necessary Vthat the passage be straight and indeed it is preferred that" it shouldl Thus, in the preferred structure the passage is folded back upon itself into a compact not be.

reactor. f

When a plurality of passages are employed in j 5 5 parallel, they should be connected frequently with tional area of reaction zone, to space velocity;

designate the portion of the reaction apparatus is employed, frequent opportunity to mix the gases from the several lateral sections of' the passage should be provided. A single passage 1%" x 4%" in cross-section needs no such mixing but if the 4%" dimension is increased to. say, several feet, such mixing should be eiected.

The apparatus should be constructed with due regard for the output desired. For most satis.

factory operations the value of SVsoo should lie between 200 and 400 and the value of MV should lie between 2000 and 8000.

In the oxidation of benzene to phenol it is desirable to present a minimum of surface commensurate with adequate temperature control. Since heat transfer between the reaction mixture and the surface of heat cumulative material is relatively slow where the temperature difference between the gas and surface is small, it is not desirable to provide sumcient surface to bring the mixture into substantial temperature equilibrium with the surface with which it is, at the instant, in contact, but it is desirable that a rather wide average temperature diffcrence between gas and adjacent surfaces exist. This average inthe portion of the reactor where substantial reaction occurs is preferably in the neighborhood of 20 to 35 centigrade degrees. the average being calculated by determining the difference between the average temperature'of the gas in'succeeding half cycles and taking half of this difference as the average temperature difference between gas and heat cumulative material. Since the coeiilcient of heat transfer increases with an increase in the average linear gas velocity, the most satisfactory area of exposed surface depends upon the space velocity and length of the reaction zone. Thus, for the space velocities mentioned, it is desirable that the sur- Figs. 3 and 4 the value for' A.' where Lsq=L/2.'

may be about e 2 0.9 allillpg In order to provide exibility of operation,it is preferable that the design features specified for thenormal reaction zone be extended to parts of the apparatus 'substantially beyond this zone. To illustrate this point it may be observed that normally around or more of the oxidation occurs within that portion of the reactor showing to consider that the apparatus exhibiting an average temperature within about 200 C. of the maximum is the reactor and should embody the same structural details as the central section.

In the operation of the type of apparatus considered above for the production of phenol from benzene, the reaction mixture passes through the reactor at a gradually rising temperature as it approaches the center of the reactor and at a gradually falling temperature as it leaves the reactor. Gas temperatures along the gas passage Vat any single instant thus describe a temperature gradient having a maximum, or crown, near the center of the reactor. The average gas temperature at any point may be determined by obtaining the instantaneous gas temperatures at thai point at suitable uniform intervals 'of time and face area, A, expressed in square feet per cubic foot of free space should lie between 2 analog for-example c v Y where L represents the' length of the reactor pas?k1 dividing the sum of the temperature readings by the number of readings. In normal operations the average gas temperature gradient for a half cycle has its crown t'o leeward of the thermal center of the reactor. Thus the instantaneous gas temperatures for afull cycle of operation may be represented by a mobile temperature gradient having its crown moving first toward oneend of the reactor, then toward the other. The thermal center ot the reactor may be determined by plotting `the average gas temperatures for a full cycle vertically versus length of the'reactor horizontally and observing the point to the right and left of which the gradient embraces equal areas. VThis point may be regarded as the thermalcenter. Normally it coincides with the point of maximum average gas temperature and the point of maximum average temperature of heat cumulative material. It normally willbe about equally spaced from the ends ofthe reaction passage but need not be at this point. In order that the process may be kept within proper bounds. the direction of gas flow should be reversed at' intervals each no longer than sumcient to generate as heat of reaction 20 times the heat'capacity of that part of the heat cumulative material whose average temperature is within C. of the maximum average temperature.

` .While-the process of the present invention is rapplicable to the vapor phase oxidation of benzene to phenol-in general, it is particularly adapted for operations at high temperatures, e. g. operations involving average thermal center temperatures between 600 and 800I C. Vperatures are the temperatures at which the oxidation proceeds rapidly and smoothly at pressures near atmospheric pressure. e. g. between 0.5

reilectthis change. Thus, forthe conditions of 76' and5.0 atmospheres absolute, but at which the These temordinary equipment commonly used for reactions such as the oxidation of hydrocarbons, is unsuitable. f Y

'I'he practical application of-the present invention may be more fully understood from thefollowing detailed discussion and appended draw-v ings. In the drawings,

Fig. 1 is a schematic diagram of suitable appa` ratus for carrying out the invention; and

Figs. 2, 3, and 4 are reactor temperature gradients for various operations to behereinafter described.

With especial reference toFig. l of the drawings; the illustrated assembly for conducting the process involves a reactor I connected at opposite ends with conduits 2 and 3 leading to regenerators d and'5 and connected at its center with conduit 5a.

As will be apparent from a consideration of the dimensions given later, reactor i has been shown somewhat out of scale to better illustrate its fundamental structure. y The reactor comprises a labyrinthine chamber divided by partitions into tiers, each of which is further divided into a series of groups of parallel passages so arranged that gases from the parallel passages of each group intermingle before passing into the passages of the next succeeding group. In the drawings the exterior walls of vthe reactor have been removed from the rst few tiers to show the internal construction more clearly. Thus, it may be seen that the first tier into which conduit 2'leads comprises a partition o, which is common to the iirst and second tiers, and a plurality of short cross-partitions 'I `and long cross-partitions 8. Each pair of 'partitions I is separatedfrom the next pair by one of the long partitions 8 and each of the long*4 partitions o is staggered withrespect to the next. This arrangement provides for viiow of three parallel streams of gas up in front of the near partition 8 to the top, where the three streamsare mixed and redivided, down between it and the far partition 8' to the bottom, where the streamsare mixed again and divided anew, and up 'againbe hind the far partition v8. On thefarside of the far partition 8 partition 8 is cut awayat the top to vpermit passage of vgasinto the second tier of the reactor.*'I'he 'gas passes "as a group of parallel streams through a series oi groups of parallel passagesin the secnd tier; 'alternately down, up; down, and finally out at 9 to the next tiert and soon 'through the apparatus, with mixving of the 'gas streams at eachchange 4of direction.

Innumerable variations iin'reactor' design are conceivable'but fundamentally thereactor com# prises al..series -of individual passages or a series of groups of parallel passages, 'each passage being defined by heat cumulative material and being relatively longcompared with one cross-sectional dimension'and relatively short compared with" the total1ength`of-the ser1es; and aplurality` ofI 'mixing zones 'for intermingling the gases from variousparts of the individual passage 'or from various .passages of a group, between each passage or group and the next in series. 4

The reactor may be constructed of'iirebric kof which there are a number of types available.

A typical analysis of a suitable iirefbrick is about k61.7% siuajaboutiaam, ammini and titanic, and 2.8% ferricoxiue. such bril-.kaars marketed inch thickness, so that the wall thickness is the same as the brick thiclmess. Preferably, courses leakage between tiers is in fact beneficial since' it tends to spread out the zone of maximum temperature. The entire reactor may be surrounded with several courses vof fire-brick or insulating brick or both, and a metal shell may be provided to avoid gas leakage from or to the system.

The internal construction and 5 may be similar to the construction of reactor I. However it is preferable to employ as regenerators iirebricklined chambers randomly packed with broken'iirebrick,'for example 1" to 2" lump fragments, providing azone of tortuous iiowthrough a mass of heatcumulative material in each regenerator. Such regenerators are relatively inexpensive toconstruct, and occupy cori-` siderably less space than regenerators of the same, heat transfer and storage capacity constructed.

like reactor I. Since the temperature-time relail even with the relatively extensive surface contact area provided by lf' to2" lump packing`, the

advantages 'of maximum heat transfer per unit with a valve-controlled inletpipe I5 for washing liquid, Asuch as benzene, and an outlet conduit I6 for gas, and Lat the bottom with an outlet pipe I'I for'liquid. Outlet conduit I6 is provided with a branch Ilfor .leading oi gas from the system and with `a valve-controlled branch I9 for leading` air or benzene vapor air mixture into the system. Conduit I8 isconnected with regenerators l and 5 -by valve-controlled conduits 20 and 2i, respectively. Gas ow from tower I4. is controlled by a two-'way valve Ilia, which may be adjusted to direct-all or a definite proportion of the gas through branch I8. v

follows:

is introduced through conduit 15a into reactor `I and drawn outthrough regenerator 5 andgconduit I I'by blower I2 and exhaustedto'the atmosphere. (Instead of y passing combustion gases, 4through 4 tower Il, they' maybe expelleddir'ectly to the atmosphere.) 'I'his heating up. is continued `until the right-hand portion vof. rea a.ctor^liv-has ,been heated to the desired reaction temperature. aiBy flowl then is directed lfrom-the reactor.. through the regenerator l and conduit I0 to warm upv this; section of the apparatus. Since in the mst A half-cycle of .actual :operationy Leregenerator''1-5 by laying these bricks, preferably those of 21/2 It isrdesirabllfthat of regenerators E ltionship in regenerators 4 and 5 does not cause 4 material loss of benzene or phenol in these units of volume may be realized without sacrice of x The operation ofthe above. apparatus isfas l For the-initial heating up, hotcombustio gas proper controll of the valves -on :lines I `andl, If.

erator l4 as a cooler for reaction products, regenerator 4 requires much less heating than regenerator 5.

After the reactor and regenerators have been heated to operating temperatures, the valves on conduits I9 and 2| are opened to permitflow of air and benzene vapor successively through regenerator 5, reactor I, regenerator I, conduit I0, blower I2, and tower Il. The rate of flow should be sufficient to leave 5% to 10% of i'ree oxygen in the exhaust gas. At the same time sufiicient4 now of benzene is provided in tower Il to wash phenol from the reaction mixture. Fresh benzene vapor air mixture is introduced continuously through conduit I9 and washed product gases, now saturated with benzene and preferabhr still at a temperature of 50-60 C., are led ou through conduit I8 for further treatment. The proportion oi' the total reaction mixture led oil at I8 may vary from only a minor proportion up to all. In general it is desirable to bleed at a suillcient rate to maintain the tree oxygen content of exhaust gas above 5%.' The ilow of reaction mixture through the reactor from right to left may continue for one minute, two minutes, four minutes, or such other period as is desired lor each half-cycle; At the endof this period the valves on conduits Iii and 2i are closed and those on I I and 20 are opened to cause a reversal of direction of ilow .so that benzene vapor air mixture ilows successively through regenerator I, reactor I, and regenerator i to tower Il. By

employing a blower on the outlet side of the reactor the reactor maybe maintained at subatmospheric pressure, for instance an absolute pressure between 14.0 and 14.6 pounds per square inch', and thus if any leakage occurs in the reactor I or regenerators 4 or t, the leakage causes passage of air into the system rather than passage of benzene or phenol vapor out therefrom to the atmosphere. y

Benzene and phenol are withdrawn through outlet pipe I1 continuously and may be processed in a continuous column to separate benzene, phenol, and other products.

Fig. 2 shows representative temperature gradients for normal operating conditions in a re` actor generally similar to that illustrated in Fig. 1 of the drawings.

The reactor comprised six parallel passages each about 43 feet long-with a cross-section of i.39"x4%". with seventeen mixing spaces disposed at approximately equal distances along the passages. The passages were defined by 11/4" x4l" x9" boron-oxidecoated tire-clay brick providing a wall thickness of 1% inch.

An air benzenevapor mixture comprising air and benzene in a mol or volume 'ratio o! about 1.05 was passed through'the reactor at an hourly mass velocity oi about 1812 and at an hourly space velocity of about 218 (BTP) based on total ireespaceinthereactonanddircctionofnow wasreversedeveryoosecondstoprovideaz-mm utcoperating cycle. o

In illustrstivellimwhichwasofaboutle h duration, about A92.4% o! the bensene inliquid -by-products (chiey diphmyl), and gasby-products was about as follows: l

Benicasimliquidby-rurmiucts.` 35

o! a composite ci-snot exit ples showed au average exit gas composition. by volume, as follows: A

With especial reference to the values plotted in Fig. 2, temperatures wereA determined at a number of points along the reactor passages and these temperatures (expressed in degrees centigrade) were plotted against their distance from the center of the reactor (expressed in feet).

Thev gradients o and b are the average gas temperature gradients for representative hallcycles, a showing the average gradient with gas flow from left to right (on the diagram) and b showing the averagesgradient with a reverse direction of gas iiow.

A word of caution is necessary with respect to the interpretation of observed values. Normally temperatures measured by thermocouples within the reactor do not indicate accurately the prevalent instantaneous gas temperature at the instant of reading since the thermoeouples are ailected not only bythe gas temperature but also by the temperature of the walls from which or to which the-thermocouple acquires or loses heat and by Gradient c is the average gas temperahn'e' gradient for a complete cycle and cloly approximates the average wall temperature since heat Aloss through the walls is negligible.

$5 The locations ol gradients a, b and c illustrate that, ilrst, the average gas temperature durins eachhalt'cyclerisestoa maximumwhichissubstantially higher than the average reactor (wall) o temperature maximum; second, the point of maxhence the halt-cycle average gas temperature 06 maximum is forward in the direction ot gasilow or leeward o! the average reactor temperature maximum: third, the thermal center in the re actor employed in the test closely approximated the physical center of the gas passages, i. e. was

l approximately equidistant from the two ends. Itis of interest'that about one-fourth of the' total heat evolved in the reactor is evolvedin two hotsoneswithinabouttwoteet ofthetwocrowns olfcurvesaaxidb (inthesectionofthereactor Bcnsene to gaseoil.byfpi'oducts 32 `-7l between Gi and loiieet to the right o! the 'dients obtained by correcting observed values to center for the periods represented by curve a). Hence, especial care should be given to the provision, -in these zones, of adequate heat storage capacity for the desired operating cycle. The reactor should be constructed to provide a heat capacity in each of these of reaction section, or hot zones, of atleast 0.01H where H represents the total heat of reaction evolved in the reactor per half-cycle. It is advantageous to provide a reasonably uniform heat capacity in that part ofthe reactor within about 80 C. of the average reactor temperature maximum and hence the heat capacity ofV this entire zone, which ordinarily may be around 3 to 5 times as long as the two hot zones together, may be around 0.06H to 0.1H, referred to centigrade temperature scale. Fig. 3 Shows representative temperature gradients in a reactor of the same size as that used in collecting the data for Fig. 2 but having the bafiles rearranged to provide two passages each about 130 feet long. Gradients f and g are half.

cycle average'gas temperature gradients for flow toward the right and left (of the drawing) respectively, and gradient h is the average wall tein-l perature gradient or whole cycle average gas temperature gradient. o Since the cross-sectional area in the 2-passage' apparatus, to which the gradients of Fig. 3 apply, is only one-third the cross-sectional area in the -passage apparatus, to which the gradients of Fig. 2 apply, the hourly mass velocity for Fig. 3 is 4836 compared with 1612 for Fig.' 2 and the resulting proportion o! benzene reacted is about 5.1% compared with 7.6%. From Figs. 2 and 3 it canbe seen that at the point of maximum halicycle average gas temperature the temperature difference between gas and adjacent walls averages from .to 35 C. for the 6passage unit and between 20 and 25 C. for the 2-passage unit. The smaller temperature difference in the latter case is due to the higher coeillcient of heat transfer resulting from the higher mass velocity and consequently smaller proportion of benzene reacted inthe latter case.

Fig. i shows gradients resulting fromI varialonger gas passage and correspondingly reduced cross-section.

Gradiente i and :I are the half-cycle 'average I gas temperature gradients in an apparatus 'of the. same length and cross-section as iniiiig. 3 but with the cross-section re-proportioned to reduce theratioyoi exposed surface area in square feet from about 15 square feet to about 85/3 square feet per cubic foot of free space.

Gradients k and l illustrate a method of secur ing in apparatus of the type involved in the operations represented in Fig. 3 results similar. to those represented by gradients i and 1i.l The gradients k and l are obtained by operating the apparatus of. Fig. 3 at the same 'gas velocities employed for producing gradients i and 1 except o that the gas stream is split and about 5.7% of the total, at about 60 C., is introduced directly into the center of the reactor. Comparing gradients i and kit will be seen that gradient'k rises more rapidly and thus at the center point of Vthe reactor, beforeaddition of cold gas. is substantially above gradienti. The addition of the cold mixture chills the reaction gasesand thus causes Athe gradient k to drop below gradienti. It then rises again but to a maximum substantially lower than it would have reached had the total quantityof air-benzene vapor mixture been It w08 25 introduced at I9.

The injection cooling method employed for gradients k and l has beenfound to be a highly satisfactory regulating method for correcting temporary maladjustments in ordinary operations. Thus, if the oxygen content of the exit gases begins to decrease substantially, injection of a small proportion of relatively cold fluid, such as liquid benzene, benzene vapor, steam, tail gas, reaction mixture, or other fluid of low free oxygen 10 content, at 5a in Fig. 1 serves to correct excessive 'temperatures and to restore proper conditions, which are reflected in a quite constant free-oxygen 4content of the exit gases, lying preferablyr between 5% and 10% by volume.

le Other methods of temperature control which havebeen found effective for handling abnormally high temperatures in the converter comprise recirculation of tail gases in varying proportions. Thus, in the event the temperature E0 rises in reactor Las indicated for example by a decrease in oxygen concentration of tail gases from a normal of 9.7% to 9.0% by volume, valve Y tained by increasing the benzene:air ratio by I0- suitable control of the benzene vaporization.

Conversely, if the temperature of reactor l becomes too low, as indicated for example by an increase in'the exit gas oxygen concentration to say 10.2%, the air concentration oi'V the entering mixture may be increased by reducing the xproportion of tail gas recirculated ci' by reducing the proportion of benzene vaporized into the mgoing air. v

Thus the control of temperature may be ren- 40 dered automatic by provision of an oxygen analyzer on the exit gas stream adapted to control theproportion of air in the mixture entering the reactor. An analyzer `effective for this purpose may be a catalytic combustion unit and thermostat control. Since the temperature of the gases tions in design and control to ycompensate for a leaving the catalytic converter unit rises with an increase of oxygen "concentration and falls with av decrease thereof, the thermostat provides-an oxygen-concentration-responsivecontrol means.

i The 'catalytic combustion unit should be supvuniform-outlet gas temperature therefrom and thusa substantially constant benzene content, a small proportion of this mixture maybe passed 2 to the analyzer and used for the catalytic combustionwithout addition of extraneous combustible.l Instead of a catalytic or flameless combustion unit, a simple name may be employedand the flame temperature used to control a thermostat. f. i

In the appended claims space velocity, SV, is

55 expressed as cubic feet of gas at standard temperature and pressure per cubic foot of reaction space (free space) per hour; and mass velocity, MV, is expressed as pounds of reaction mixture per hour per square foot of cross-sectional area (free space) of reaction zone.

I claim: 1. In the manufacture of phenol by vapor phase oxidation ot lbenzene, the improvement which comprises passinga mixture comprising 76 benzene vapr and oxygen through a three unit intermediate unit B packed with heat cumulative material distributed to provide a substantiallyhigher ratio of free'space to contact surface than umts A and C and to direct flow of gas serially through a plurality of individual passages with intermediate mixing, maintaining unit B as gas' temperatures represented by a temperature gradient exhibiting a maximum, passing said benzene vapor oxygen mixture through the units of said system alternately in the orders A, B, C and C, B, A whereby the aforesaid maximum is shifted toward C and toward A respectively, and controlling the frequency of alternation so as to maintain said maximun'iwithin unit B.

2. In the manufacture of phenol by high temperature vapor phase oxidation of benzene, the improvement which comprises passing a mixture comprising benzene vapor and oxygen at an absolute pressure vbetween 0.5 and 5.0 atmospheres through a three unit system comprising two units A and C Veach packed with heat cumulative material distributed to direct a tortuous flow of gas therethrough and an intermediate unit B packed with heat cumulative material distributed to provide a substantially higher ratio of free space to contact surface than units A and C and to direct flow of gas serially through a plurality of indi@ ratio through unit B having a numerical value of -at least 2, maintaining unit B at temperatures represented by an average surface temperature gradient exhibiting a maximum between 600 C. n and and 800 C., said benzene vapor oxygen mixture through the units of said system alternately in the orders A. B, C and C, B, A, whereby the instantaneous maximum gas .temperature is shifted toward C and toward A respectively, and

controlling the frequency of alternation so as to maintain the instantaneous maximum gas temperaturewithinunitandsoastomaintain the average surface temperature maximum in degreescentigravzieinunitaAandCnothigherl ing unit B at temperatures represented by an average surface temperature gradient exhibiting a maximum between 600 C. and 800 C., passing said benzene vapor oxygen mixture through the units of said system alternately in the orders A, B, C and C, B, A at an hourly space velocity between y200 and 400 and an hourly mass velocity between 2000 and 8000, whereby the instantaneous maximum gas temperature is shiftedtoward C and toward A respectively, and controlling the frequency of alternation so as to maintain the instantaneous maximum gas temperature within unit B and so as to maintain the average surface. temperature'maximum in degrees centigrade in units A and C not higher than the average surface temperature maximum in unit B minus 80. A 4. In the manufacture of phenol by high temperature vapor phase oxidation of benzene, the

L, of the series of passages being suiicient to provide an MV S V ratio through unit B having a numerical value of at least two, and the spacing of said vfire-brick being such as to provide an exposed surface area'. expressed in square feet per cubic foot of free space, between 2 i antilog (1 -og L) 2 2 N8 (im) where L is expressed in feet, and two. units A and C each comprising randomly packed refractory disposed-so as to provide a substantially greater ratio of exposed surface area to free space than unitB, maintaining unit B at temperatures represented by an average surface temperature gradient exhibiting a maximum between 600 C. and 300 C., passing said benzene vapor air mixture through the units of said system alternately in the orders A, B, C, and C, B, A at an hourly space velocity between 200 and 400 and an hourly mass velocity between 2000 and 8000 whereby the instantaneous maximum gas temperature is shifted between 0.5 and 5.0 atmospheres.

pressures A throughatbreelmit comprisingaunitB packed with heat cumulative material disposed soastoprovldeenexposedsurfacearea,

when L deuils in reet. and :we mass ssamm faceareatofreespaee thanunitiBand-todirect toward C and toward A, respectively, and controlling the'frequency of alternation so as to generate as heat of reaction in each flow period not morethanxotimes the heatcapacityofthefirebrick within 8 0" C. of said average surface temperature maximum and to thusxmaintain the instantaneous maximum gas temperature within unit B, and the average surface maximum-indegrees centisradein unitsAandC not higherthan the average surface temperature maximum in unit Bminus 80.

5.k In the of phenolby vapor phase' oxidation of benzene, the improvement which vapor-and oxygerrtim'oughV a hot reaction sono sages within the heat-cumulative material, the

Yatortuousiiowofges th'ltdmcunfhebmnmdmamis amenace ratio through said section having a numerical value of at least .1.4, within said section of heatcumulative material repeatedly intermingling all the gases iiowing through the plurality of passages in the heat-cumulative-material and dividing the intermingled gases into separate streams which are again passed in contact with the heatcumulative material, maintaining a suiiicient flow of said benzene vapor-oxygen mixture to shift the'instantaneous maximum gas temperature forward in the direction of gasow Substantially beyond the locus of said average wall surface temperature maximum, then reversing the direction of -gas flow and maintaining suflcient iiow to shift said maximum gas temperature forward in the new direction of gas flow substantially beyond the locus of said average wall surface temperature maximum and repeating said reversal of gas ow at intervals correlated so as to maintain the zone of maximum instantaneous gas temperatures centrally disposed with respect to said heat cumulative material.

6. In the manufacture of phenol by vapor phase y oxidation of benzene, the improvement which comprises. passing a mixture comprising benzene vapor and oxygen through a reaction zone con-l taining heat-cumulative material wherein said mixture passes through a pluralityof passages within the heatecumulative material, heat of re= action of the benzene and oxygen is absorbed by said material and the average temperature gradient of said material exhibits a maximum, the length (along the direction of gas ow therethrough) of that portion of the heat-cumulative ymaterial which is at temperatures within 200 centigrade degrees of said maximum being so correlated with the rate at which said mixture is passed through said portion of the heat-cumulative material that the ratio SVM has a numerical-value of at least 2, within said portion of heat-cumulative material repeatedly intermingling all the gases iiowing through the plurality of passages in the heat-cumulative material and dividing -the interming'led gases into separate streams which are again passed in contact with the heat-cumulative material, maintaining a sufficient flow of said benzene vapor oxygen mixture to shift the instantaneous maximum gas temperature forward in the direction of gas ow substantially beyond the locus of said average temperature maximum, then reversing the direction of gas ow yand maintaining sutilcient ow to shift said. maximum gas temperature forwardin the new direction of gas iiow subof gas flow at intervals correlated so as to maintain the zone of maximum instantaneous gas temperatures centrally disposed with respect to said heat-cumulative material.

` FRANK PORTER. 

